Mono-azo dyestuffs



Patented Apr. 25, 1939 UNITED STATES PATENT oFFle aissass MONO-AZQDYESTUFES iedrich Felix and Wilhelm Huber, Basel, Switzerland,as'sig'nors' to the firm of Society of Qhemical Industry in Bas le,Basel, Switzerland No Drawing. Application N ovember 15, 1937, Sc-

11 N9? 11 ece e' e 3 Claims. (01. 2 -207) This invention relates to newmono-azo-dyestuffs and more particularly it relates to azo-dyestuffswhich may be represented .by the formula:

Z I N0 =N N CN' R1 wherein :1: represents hydrogen, alkyl, benzyl orphenyl, y represents alkyl or benzyl, R1 represents an acylatedamino-group and R2 halogen, alkyl, alkoxy or an acylated amino-group and2 represents hydrogen, halogen or nitro.

The term alkyl embraces .unsubstituted alkyl ll; groups as ,well assubstituted .alkyl groups.

The new azo-dyestufis are dark powders when dry. They dissolve inorganic solvents, for in stance pyridine, to red, violet, blueo-r greensolutions and, when suitably dispersed dye cellulose esters and ethersas well as laquers produced on .their basis red, violet, blue or greentints.

As coupling components there come into ques: tion amines which containin 2-position or in 2- and in 5-position a further acylated aminogroup.Advantageously, the amino-group in 1- position should contain at leastone alkyl, ar'alkyl or aryl residue, those alkyl residues beingespecially suitable which carry hydroXyl-groups capable ofetherification or esterification. They may,

.0 however, also contain other substituents, 'for instance halogen;cyanogen, sulfone-groups or the like.

' As further substituents of non-acid nature (R2) there are especiallysuitable alkyl, hydroxy- .35 alkyl or aralkyl groups; also alkyloxygroups,

halogen atoms, hydroxy groups or the like may be present. Of thesecompounds the following may be named: 1-amino-3-acetylaminobenzene, 1 4N -(dihydroxy-ethylamino) 2 -methoxy- 5 $0 acetylaminobenzene, -1-N-bis-(dihydroxy-prop-ylamino) -2-methoxy-5-acetylaminobenzene, l-N- (diethyl)amino-Z-methoxy -5-acetylaminobenzene, l- N- (dimethyl) -amino 2-methoxy- 5 -acetylaminobenzene. The alkyl'residues may also bedifferent, for instance 1.N-(methyl-hydroxyethyl) -amino.-2 methoxy-fieacetylaminobenzene may be used. The hydroxy-groups may be etherified bymethylor ethyl-groups; alternatively they may be esterified by means oforganic acids,

so for example formic acid, acetic acid or by means of inorganic acids,for example sulfuric acid. There are further suitable compounds likel-N- alkylor -dialkylamino-2-alkoxy-5-hydroxyalkylacetylaminobenzenes,for instance l-N-(dimethyl) amino -2-methoxy-5-hydroxyethylacetylaminobenzene, 1N- (dimethoxyethyl) -amino- 2-methoxy- 5 hydroxyethylacetylaminobenzlene, 1 -N- (dimethoxyethyD-amino- 2 -methoxy -5 -dihydroxypropylacetylaminobenzene or l-N-(alkylor dihydroxyalkyl) amino-2 5 diacetylaminobenzenes.

as m components there may be used 1-.

Example 1 16.3 parts of 4-nitro-2-cyano-1-aminobenzene are diazotized inusual manner by means of a nitrosyl sulfuric acid corresponding with 6.9parts of sodium nitrite in concentrated sulfuric: acid. '80 soon as asampledissolves clearly inice water, the mass is poured into ice water'andthe diazo solution thus obtained is coupled with ajsolution of 26.8parts of l-N-(dihydroxyethyl)-=amino 2- methoxy-5-acetylaminobenzene indilute hydrochloric acid. The coupling is brought to a finish by addingsodium acetate: The dyestuff thus 0-btained of the formula:

is a dark powder whendry; it dissolves in organic solvents for instanceethyl acetate and acetone, to a reddish blue solution; when suitablydispersed it dyes acetate artificial silk reddish blue tints.

' Similar dyeing dyestufls are obtained bythe reaction ofdiazo-compounds from 4-nitro-2- cyano-l-aminobenzene with"l-N-monoethyl-2- methoXy-5-acetylaminobenzene,' l-N-jm'onooctodecyl-2-methoxy-5-acetylaminobenzene, 1-N-di- .16 there maybe obtained in par- Ewample 2 16.3 parts of1-amino-2-cyano-4-nitrobenzene are diazotized as described above bymeans of nitrosyl sulfuric acid and the diazo solution obtained iscoupled with a solution of 29.6 parts of l-N- (dimethoxyethyl)-amino-2-methoxy-5- acetylaminobenzene in dilute hydrochloric acid. Thedyestufi obtained of the formula:

I /CH2CH2O CH:

omcmo CH:

CN v IIIH CO is a dark powder when dry; it dissolves in organic solventssuch as acetone or ethyl acetate to a reddish blue solution and dyesacetyl cellulose in the mass pure reddish blue tints.

By coupling the diazo-compound of the above base with1-N-ethyl-hydroxyethy1-2-methoxy-5- ethylaminobenzene,l-N-methyl-hydroxypropyl- 2-methoxy-5-acetylaminobenzene, orl-N-ethylmethyl-2-methoxy-S-acetylaminobenzene, there are obtaineddyestuffs having similar properties. Instead of the above componentsthere may also be used l-N-ethyl-dihydroxypropyl-2-ethoxy-5-benzoylaminobenzene, l-N-dihydroxypropyl-Z-ethoxy-5-benzene-sulfaminobenzene or l-N-dibutyl-2-methylor-2-chloro-5-methyl-sulfaminobenzene. All these dyestuffs are darkpowders dissolving in pyridine to red, violet, blue and green solutionsand dyeing esters and ethers of cellulose and lacquers produced on theirbasis the same tints.

Example 3 I 19.75 parts of 1-amino-2-cyano-4-nitro-6- chlorobenzene arediazotized by introduction into an ice-cooled solution of nitrosylsulfuric acid corresponding with 6.9 parts of sodium nitrite inconcentrated sulfuric acid and the diazo solution thus obtained iscoupled with a solution of 26.8 parts of l-N-(dihydroxyethyl)-amino-2-methoxy-5-acetylaminobenzene in dilute hydrochloric acid. The couplingis completed by addition of sodium acetate. The dry dyestufi thusobtained of the formula:

is a dark powder soluble in organic solvents, for instance ethyl acetateor acetone to a greenish blue solution and dyes acetate artificial silkpure sapphire blue tints when the dyestufi is in a suitable stage ofdispersion.

A similar dyestufi is obtained by using l-amino- 2-cyanoAnitro-fi-bromaniline as the diazotizing component.

Dyestuffs soluble organic solvents are also obtained by coupling thediazo-compound from 1-amino-2-cyano-4 fi-dinitrobenzene or1-amin0-2-cyan0-4-nitro-6-brom0- or -6-iodobenzene with the baseindicated in this example. 5 This base can also be replaced .by otherbases, for example I-N-dimethyl-2 5-diacetylaminobenzene, 1 Ndimethyl-2-formylamino-5-ethoxyaminobenzene, 1-N-diethyl-25-diformy1aminobenzene, l-N-dihydroxyethyl-Z-methoxy-5-formy1- 10aminobenzene, l-N-dimethyl-Lmethysulfamino- 5-acetylaminobenzene orl-N-dimethyl-ZzS-diethylsulfaminobenzene.

from

Emample 4 19.75 parts of 1-amino-2-cyano-4=-nitro-6- (ill v ()CHa (5N HI QHaCHaO CH:

is, when dry, 2. dark powder soluble in organic solvents such as acetoneand ethyl acetate to a v greenish blue solution and dyeing acetylcellulose 35 in the mass pure sapphire blue tints.

When coupling the diazo-compound of this example withl-N-ethyl-p-chloroethyl-Z-methoxy-5-acetylaminobenzene,l-N-ethyl-p-cyanoethyl-2-methoxyaminobenzene orl-N-hydroxyethyl43-cyanoethyl-2-ethoxyaminobenzene, there are obtaineddyestuffs having similar properties.

Example 5 10 parts of the dyestuff described in Example 3 are stirred toproduce a uniform paste containing 20 per cent of dyestuff with asuitable dispersing agent such as Turkey red oil, sulfitecelluloseliquor or sulfonation products of the residue from the manufacture ofbenzaldehyde. 1 50 part of this paste is intimately mixed with 10 partsof water at 50 C. and so much of a concentrated soap solution as willproduce in a dye bath prepared with the paste a solution of soap of 2per cent strength, The mixture is then diluted with about 300 parts ofcold water. Into the emulsion thus prepared are entered 10 parts ofartificial acetate silk yarn; the goods are handled, the bath beingheated within hour to -85 0. and dyeing continued for about another 4hour at this temperature. The goods are then rinsed and brightened asusual. There are obtained vivid bright blue dyeings.

What we claim is: 5x

1. Mono-azo-dyestufis of the general formula:

halogen OOH:

l yomcmon N0Q-N=N N omomori 7 ON lTIH which dyestuffs are dark powderswhich dye ace- "(5 tate artificial silk green-blue tints of goodfastness and dischargeability.

2. The mono-azo-dyestuff of the formula:

01 OCH: 5 /OH2CH20H omomon ON IYIH 10 20 which is a dark powder whichdyes acetate arti- 3. The mono-azo-dyestufi of the formula:

Br OOH: I /C H2OH20H NO N=N N\ CHgCHgOH ON 17TH CO

